Complexes of 2-heptadecylimidazolines



United States COMPLEXES F Z-HEPTADECYLIMIDAZOLINES John N. Hogsett,Charleston, W. Va., assignor to Union Carbide Corporation, a corporationof New York No Drawing. Application March 11, 1957 Serial No. 645,018

6 Claims. (Cl. 260-299) This invention relates to complexes ofZ-heptadecylimidazolines and to a process for their preparation. Moreparticularly, this invention relates to chelates of2-heptadecylimidazolines, as new compositions of matter and to processfor their preparation.

I have discovered that novel chelates of Z-heptadecylimidazolines areformed by reacting a metallic compound with Z-heptadecylimidazoline.

An embodiment of the present invention is a class of new compositions ofmatter which are chelates formed by reacting a metallic salt with a2-heptadecylimidazoline. A specific chelate, which is illustrative ofthis embodiment of my invention is tri(Z-heptadecylimidazoline aceticacid) cerium IV hydrogen sulfate 2,881,182 Patented Apr. 7, 1959 acidsalts of Z-heptadecylimidazoline with the salts of the metals of groupII of the periodic table. Illustrative of such chelates are:di(heptadecylimidazoline acetic acid) magnesium sulfate,di(heptadecylimidazoline acetic acid) magnesium chloride,di(heptadecylimidazoline acetic acid) zinc chloride,di(heptadecylimidazoline acetic acid) cadmium sulfate,di(heptadecylimidazoline acetic acid) cadmium nitrate,di(heptadecylimidazoline acetic acid) mercury sulfate anddi(heptadecylimidazoline acetic acid) mercury bromide.

The compositions of my invention also include the chelates formed byreacting Z-heptadecylimidazoline with the salts of the metals of groupHI of the periodic table. Illustrative of such chelates are:triheptadecylimidazoline aluminum sulfate, triheptadecylimidazolinealuminum nitrate and triheptadecylimidazoline aluminum chloride.

My compositions also include chelates formed by reacting acid salts ofZ-heptadecylimidazoline with the salts of the metals of group III of theperiodic table. Illustrative of such chelates are:tri(heptadecylimidazoline acetic acid) aluminum sulfate,tri(heptadecylimidazoline acetic acid) aluminum nitrate andtri(heptadecylimidazoline acetic acid) aluminum chloride.

The compositions of my invention also include the chelates formed byreacting 2-heptadecylimidazoline with the salts of the metals of groupIV of the periodic table. Illustrative of such chelates isdiheptadecylimidazoline lead nitrate.

Still other compositions within the scope of my invention are thechelates formed by reacting the acid salts which can be represented bythe structural formula: of Z-heptadecylimidazoline with the salts of themetals H 1LT HOOCCH HOOCOH 3 C CC17Ha5 3 i in i r C17H35C CH: (llfiz(II-CHEM (H804);

-' Hz CH2"- Ce. .i

'Iri(2-heptadecylimldazoline acetic acid) cerium IV hydrogen sulfate,CacHmaOaaNaSaCB These compositions include the chelates formed byreacting Z-heptadecylimidazoline with the salts of the metals of group Iof the periodic table. Illustrative of such chelates are:diheptadecylimidazoline silver nitrate and diheptadecylimidazolinecopper sulfate.

My compositions also include chelates formed by reacting the acid saltsof Z-heptadecylimidazoline with the salts of the metals of group I ofthe periodic table. Illustrative of such chelates are:di(heptadecylimidazoline acetic acid) sodium sulfate,di(heptadecylimidazoline acetic acid) sodium hypophosphate,di(heptadecylimidazoline acetic acid) silver nitrate,di(heptadecylimidazoline acetic acid) copper sulfate.

The chelates of my invention can also be formed by reactingZ-heptadecylimidazoline with the salts of the metals of group II of theperiodic table. Illustrative of such chelates are:diheptadecylimidazoline zinc nitrate, diheptadecylimidazoline zincchloride, diheptadecylimidazoline cadmium sulfate,diheptadecylimidazoline cadmium nitrate, diheptadecylimidazoline mercurysulfate and diheptadecylimidazoline mercury bromide.

My chelates also include those formed by reacting the of group IV of theperiodic table. Illustrative of such chelates isdi(heptadecylimidazoline acetic acid) lead nitrate.

Other compositions within the scope of my invention are the chelatesformed by reacting Z-heptadecylimidazoline with the salts of the metalsof group VI of the periodic table. Illustrative of such chelates are:trihepta decylimidazoline chromium sulfate, triheptadecylimidazolinechromium nitrate and triheptadecylimidazoline chromium chloride.

Still other compositions of my invention are the chelates formed byreacting the acid salts of Z-heptadecylimidazoline with the salts of themetals of group VI of the periodic table. Illustrative of such chelatesare: tri(heptadecylimidazoline acetic acid) chromium sulfate,tri(heptadecylimidazoline acetic acid) chromium nitrate and tri-(heptadecylimidazoline acetic acid) chromium chloride.

Other compositions within the scope of my invention are the chelatesformed by reacting Z-heptadecylimidazoline with the salts of the metalsof group VII of the periodic table. Illustrative of such chelates are:diheptadecylimidazoline manganese nitrate, diheptadecylimidaz olinemanganese chloride and diheptadecylimidazoline I manganese sulfate.

The compositions of my invention also include chelates formed byreacting the acid salts of Z-heptadecylimidazoline with the salts of themetals of group VII of the periodic table. Illustrative of such chelatesare: di(heptadecylimidazoline acetic acid) manganese nitrate,di(heptadecylimidazoline acetic acid) manganese chloride anddi(heptadecylimidazoline acetic acid) manganese sulfate.

Another group of compositions within the scope of my invention are thechelates formed by reacting 2-heptadecylimidazoline with the salts ofthe metals of group VIII of the periodic table. Illustrative of suchchelates are: triheptadecylimidazoline iron sulfate,triheptadecylimidazoline iron phosphate, triheptadecylimidazoline ironnitrate, triheptadecylimidazoline cobalt sulfate anddiheptadecylimidazoline nickel nitrate.

Still another group of compositions within the scope of my invention arethe chelates formed by reacting the acid salts ofZ-heptadecylimidazoline with the salts of the metals of group VIII ofthe periodic table. Illustrative of such chelates are:tri(heptadecylimidazoline acetic acid) iron sulfate,tri(heptadecylimidazoline acetic acid) iron phosphate,tri(heptadecylimidazoline acetic acid) iron nitrate,tri(heptadecylimidazoline acetic acid) cobalt sulfate anddi(heptadecylimidazoline acetic acid) nickel nitrate.

Other compositions within the scope of my invention are the chelatesformed by reacting Z-heptadecylimidazoline with the salts of the metalsof the lanthanum series of the periodic table. Illustrative of suchchelates is tri- (heptadecylimidazoline) cerium acid sulfate.

Still other compositions within the scope of my invention are thechelates formed by reacting the acid salts of 2-heptadecylimidazolinewith the salts of the metals of the lanthanum series of the periodictable. Illustrative of such chelates is tri(heptadecylimidazoline aceticacid) cerium acid sulfate.

The compounds of the present invention can be prepared by a processwhich comprises bringing a Z-heptadecylimidazoline into reactiveadmixture with a metal salt under conditions to produce a chelate.

The metal salts which are best suited for use in this invention arewater-soluble. For this reason, the reaction should be conducted in asolvent medium which comprises at least 80 percent water. Other solventswhich can be used together with water are methanol, ethanol, isopropanoland pyridine. The two reactants, namely the Z-heptadecylimidazoline andthe metal salt, need not be added to the solvent in any particularorder. Preferably, however, in the case of Z-heptadecylimidazoline, themetal salt is dissolved in water and the Z-heptadecylirnidazoline isdissolved in an alcohol, such as isopropanol, and the two solutions arecombined. In the case of Z-heptadecylimidazoline acetic acid, bothreactants are preferably dissolved in water.

The reaction is preferably conducted at 20 to 30 C. but

can be conducted at temperatures between about C. and about 80 C.

The following example is illustrative:

EXAMPLE Tri(2 heptadecylimidazoline) cerium IV hydrogen (acid) sulfate(C H O N S Ce) was prepared as follows:

About 41.6 grams of cerium acid sulfate (Ce(HSO were dissolved in 3000ml. of water and the solution was agitated at a slow rate. To thissolution was added 100 ml. of an isopropanol solution containing 30grams of 2- heptadecylimidazoline. A precipitate formed and was filteredat reduced pressure in a large Biichner funnel. The precipitate waswashed twice with water and dried at 50 C. and mm. Hg for 24 hours. Thedried precipitate had a melting point of 184-l94 C. The calculatedpercentage composition for a 100 percent pure compound and the actualcomposition (by weight) for the cerium IV PERCENTAGE COMPOSITION OF 'IRI(Z-HEPTADECYL- IMIDAZOLINE) CERIUM IV HYDROGEN SULFATE Calculated,Percent Gom- Found, Element position Percent 3R to 1 e Composition Thedata obtained agree satisfactorily with the theoretical structure ofvthe cerium IV chelate containing 3 moles of Z-heptadecylimidazoline permole of cerium, in accordance with the accepted. coordinant number of 6for The other chelates, of this invention can be prepared in a similarmanner.

As disclosed in copending T orgeson application, Serial No. 545,107,filed November 4, 1955, the chelates of this invention are useful asfungicides. Representative chelates contemplated herein were tested forfungicidal activity by means of the slide germination test. Essentiallythis test method consisted of germinating spores in continual contact,on glass slides, with given concentrations of the chemical under test.The. germination was observed after 24 hours and the amount of thechemical needed to inhibit germination of 50 percent (LB. 50 value) ofthe spores was determined. The procedure used is more fully set forth ina paper entitled The Slide Germination Method of Evaluating ProtectantFungicides, published in Phytopathology, July 1943, vol. XXXIII, No. 7,pp. 627-632. Two different and typical fungi were used for this test.The fungi tested were Sclerotinia fructicola (Wint.) Rehm (S.f.) andAlternaria oleraceae (A.o.). The values in Table II below represent theparts by weight of the chelate under test, in a million parts by weightof liquid, to prevent the germination of 50 percent of the spores. Theliquid used, which of itself did not inhibit germination of the spores,was Lins solution, which consists of 10 grams of dextrose, 2.46 grams ofMgSO -7H O and ml. of distilled water. Ten milliliters of this solutionwere added to each 100 milliliters of spore.

The periodic table referred to in this application is the periodic tableof the elements revised in accordance with the Journal of the AmericanChemical Society, volume 76, page 2033 (1954).

This application is a continuation-in-part of my copending application,Serial No. 545,108, filed November 4, 1955, now Patent No. 2,789,115.

I claim:

1. A chelate having the structural formula MR, wherein R is a memberselected from the group consisting of 2-heptadecylimidazoline and acidsalts thereof, M is both the anion and cation of an inorganic salt of ametal of the lanthanum series of the periodic table and n is an integerhaving a value of one-half the coordination number of said metal.

2. A chelate having the structural formula MR wherein R is2-heptadecylimidazoline, M is both the anion and cation of an inorganicsalt of a metal of the lanthanum series of the periodic table and n isan integer having a value of one-half the coordination number of saidmetal.

3. A chelate having the structural formula MR wherein R is an acid saltof 2-heptadecylimidazoline, M is both the anion and cation of aninorganic salt of a metal of the lanthanum series of the periodic tableand n is an integer having a value of one-half the coordination numberof said metal.

4. A chelate having the structural formula MR wherein R isZ-heptadecylimidazoline acetic acid, M is References Cited in the fileof this patent UNITED STATES PATENTS 2,155,877 Waldmann et a1 Apr. 25,1939 2,540,171 Kifi Feb. 6, 1951 2,789,115 Hogsett Apr. 16, 1957 FOREIGNPATENTS 531,297 Germany Aug. 7, 1931 OTHER REFERENCES Klingenstein: Ber.Deut. Chem., vol. 28, pp. 1175-76 (1895).

1. A CHELATE HAVING THE STRUCTURAL FORMULA MRN WHEREIN R IS A MEMBERSELECTED FROM THE GROUP CONSISTING OF 2-HEPTADECYLIMIDAZOLINE AND ACIDSALTS THEREOF, M IS BOTH THE ANION AND CATION OF AN INORGANIC SALT OF AMETAL OF THE LANTHANUM SERIES OF THE PERIODIC TABLE AND N IS AN INTEGERHAVING A VALUE OF ONE-HALF THE COORDINATION NUMBER OF SAID METAL.